CN104844466B - Cardanol group cationic quaternary ammonium salt, preparation method and application thereof - Google Patents
Cardanol group cationic quaternary ammonium salt, preparation method and application thereof Download PDFInfo
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- WLAMQLTTYMHCPL-UHFFFAOYSA-N CC(C)C(C)(C)[N](C)(C)C Chemical compound CC(C)C(C)(C)[N](C)(C)C WLAMQLTTYMHCPL-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention discloses a cardanol group cationic quaternary ammonium salt which is shown in a following formula (I) and a preparation method therefor. In the formula (I), R is one of chlorine, bromine and iodine; T is one of C2-C10 normal alkyl, o-, m- and p-diethymethylbenzene and 4,4'-diethymethyl-benzophenone; m=2-10; n=0-6; X=chlorine, bromine or iodine. Cardanol and dihalide perform an etherification reaction, and then react with dimcthylamine and dihalide to obtain the cardanol group cationic quaternary ammonium salt. The compound shown in the formula (I) is applied in emulsion polymerization as an emulsifying agent, and also can be applied in preparation of light-cured resin as a photoinitiator. The cardanol which is fully utilized services as an ATRP initiator and the linear polymer after active polymerization further can serve as a prepolymer of light-cured resin. The polymer capable of achieving light-cured crosslinking has a wide prospect in synthesis of light-cured coatings, printing ink, adhesives and other thermosetting resin. The formula is shown in the description.
Description
Technical field
The present invention relates to a kind of novel surfactant, in particular to a kind of Fructus anacardii phenolic group cationic quaternary and its system
Preparation Method and application.
Background technology
In recent years, the crisis of fossil resource increasingly causes the attention of people, and promotes numerous scientific research personnel to find and open
Send out other substitutable resources.Wherein substitute fossil resource using Renewable resource, become one of focus of current research.Fructus anacardii
Shell oil (cnsl) is a kind of liquid component extracting from cashew nut shell, is the side-product in Fructus anacardii processing, and wherein Cardanol contains
Amount accounts for 90% about, if the liquid by-product of these pitchies is not used but be directly discharged in environment, it will to ring
Severe contamination is caused in border.About 500,000 tons of world's cashew shell oil annual production at present, is a kind of abundant, inexpensive Renewable resource.From
At present, the purposes of Cardanol is only limitted to paint, friction material field, therefore, it is studied and needs to add further with application
By force (c.j.cheng, x.x.bai, s.j.liu, q.h.huang, y.m.tu, h.m.wu, x.j.wang.j.polym.res.,
2013,doi:10.1007/s10965-013-0197-2.).
Emulsion polymerization is to prepare water paint, the important method of ink, adhesive and other polymeric material.With other side
Method is compared, and the advantage of emulsion polymerization has: one is with water as medium, and viscosity is low, it is easy to accomplish continuous operation, safe operation, no
Fire hazardous etc.；Two be low production cost, it is to avoid using the trouble of more expensive organic solvent and recycling design；Three be by
In the blanketing effect of system, it is effectively reduced double-basis and terminates, make polymerization rate and molecular weight be improved (Zhang Hong simultaneously
Great waves, yellow rose-tinted clouds. emulsion polymerization new technique and application .2007, Beijing: Chemical Industry Press .).Traditional emulsion polymerization is often
Using small-molecular emulsifier, and these small-molecular emulsifiers eventually enter in polymeric articles, and it is unfavorable to bring to product
Impact, for example, small-molecular emulsifier can make polymer resistance to water be deteriorated to surface migration, and affect the optics of product, electricity and
Surface property etc..
Atom transfer radical polymerization (atrp) is a kind of novel living radical polymerization developing in recent years, and it is dashed forward
The advantage going out shows themselves in that 1) suitable monomers species is wide；2) molecular weight distribution is narrow；3) monomer conversion and initiator cause
Efficiency is higher；4) can prepare have multiple topological structures copolymer (such as block, random, grafting, alternately, gradient, star, comb
Shape, hyperbranched, crosslinked, water solubility copolymer etc.) and homopolymer (as distant pawl, new terminally functionalized polymers etc.)；5) can be
Carry out in the difference system such as water base；6) initiator (tsarevsky, n.v. cheap and easy to get；matyjaszewski,
k.chem.rev.2007,107,2270-2299.).Particularly developed recently " electron transfer produce spike atom transfer
Radical polymerization " (aget atrp) overcomes the deficiency of traditional atrp, it is possible to use the pure tool of high-valency metal catalyst preparation
There is the copolymer of topological structure, system is no longer so sensitive to oxygen.
At present, active free radical polymerization has successfully been applied to emulsion polymerization, mini-emulsion polymerization, micro-emulsion polymerization body
In system.But, these Living Radical Emulsion Polymerizations, it is typically necessary simultaneously using corresponding initiator and traditional small molecule breast
Agent, makes troubles to operation, and small-molecular emulsifier eventually enters in polymeric articles, brings unfavorable shadow to product
Ring, for example, small-molecular emulsifier can make polymer resistance to water be deteriorated, and affect optics, electricity and the table of product to surface migration
Face performance etc..
Also known as Gemini surface active agent, its molecular structure is general by two by a linker to gemini surfactant
The class novel surfactant that the hydrophilic group of logical surfactant molecule connects together and formed.Special due to its structure
Property, gemini Surfactants exhibit has gone out the performance not available for conventional surfactants, such as: (1) is more easy to aggregation formation glue
Bundle；(2) there is lower krafft point；(3) Gemini surface active agent reduces the capillary tendency of aqueous solution much larger than generation
The tendency of micelle, thus it is more prominent to reduce the capillary efficiency of aqueous solution；(4) easily adsorb in gas-liquid surface, thus more
It is effectively reduced the surface tension of aqueous solution；(5) capillary to aqueous solution reduction efficiency and reduction ability for, Shuangzi table
Face activating agent and conventional surfactants are especially and the compounding of nonionic surfactant can produce more preferable cooperative effect；
(6) there is good calcium soap dispersibility etc..
The shortcoming of linear polymer is that mechanical strength is low, and Scratch Resistance is poor, and resistance to chemical attack is weak, easily aging etc., because
The polymer that this people often makes cross-linking type is used.But, if directly making cross linked polymer, because it belongs to only molten
Rise undissolved thermosetting resin it is impossible to for coating, ink, in adhesive.So, band is first prepared by suitable method
The prepolymer of active group, crosslinks solidification again after using construction, then has great importance.
Content of the invention
Present invention aim to overcoming the shortcomings of existing for prior art, provide a kind of Fructus anacardii phenolic group cationic season
Ammonium salt and preparation method and application.
For achieving the above object, the present invention provide Fructus anacardii phenolic group cationic quaternary it is characterised in that structural formula such as
Following formula (i):
Wherein, r be chlorine, bromine, iodine,One of；T is c2～c10Alkyl, o-, m-, to two methylenes
Base benzene, 4, one of 4 '-dimethylene benzophenone；M=2～10；N=0～6；X=chlorine, bromine or iodine.
The present invention also provides the preparation method of above-mentioned Fructus anacardii phenolic group cationic quaternary, comprises the steps:
1) dihalide of structural formula (ii) and Cardanol (iii) are carried out etherification reaction under alkali and solvent condition, obtain
Compound to structural formula (iv)；
2) compound of structural formula (iv) is reacted with dimethylamine, obtain the compound of structural formula (v)；
3) dihalide of the compound of structural formula (v) and structural formula (vi) is reacted, obtain the product of structural formula (i)；
Reaction scheme is as follows:
Wherein, r be chlorine, bromine, iodine,One of；T is c2～c10Alkyl, o-, m-, to two methylenes
Base benzene, 4, one of 4 '-dimethylene benzophenone；M=2～10；N=0～6；X=chlorine, bromine or iodine.
Step 1 of the present invention) in, dihalide used can be selected for but be not limited to 1,2- dichloroethanes, glycol dibromide, 1,
3- dichloropropane, 1,3- dibromopropane, 1,3- diiodo propane, 1,4- dibromobutane, pentamethylene bromide, 1,5- bis- iodopentane,
1,6- dibromo-hexane or 1,10- dibromo-decane；Alkali used can be but not limited to sodium bicarbonate, sodium carbonate, potassium carbonate, carbonic acid
Caesium, sodium hydroxide, potassium hydroxide, triethylamine, diisopropyl ethyl amine, pyridine, n, n- dimethyl dodecylamine, tetramethyl second
Diamidogen or n, n- dimethylethanolamine；Solvent for use can be but not limited to acetone, dichloromethane, 1,2- dichloroethanes, chloroform,
Carbon tetrachloride, acetonitrile, oxolane, 1,4- dioxane, benzene, toluene or dimethylbenzene；Reaction temperature be from 0 DEG C to solvent return
Any one steady state value, preferably room temperature in stream temperature.
Step 2 of the present invention) in, dimethylamine used by reaction can be aqueous solution can also be its hydrochlorate, hydrobromate or
Hydriodate；It is simultaneously introduced other alkali, other alkali used can be but not limited to sodium carbonate, potassium carbonate, cesium carbonate, hydrogen during reaction
Sodium oxide, potassium hydroxide or potassium phosphate；Reaction solvent for use can be but not limited to acetone, dichloromethane, 1,2- dichloroethanes,
Chloroform, carbon tetrachloride, acetonitrile, oxolane, 1,4- dioxane or be above solvent composition mixed solvent；Reaction temperature
Degree is from 0 DEG C of any one steady state value, preferably room temperature to the reflux temperature of solvent.
Step 3 of the present invention) in, reaction solvent for use can be but not limited to acetone, ether, ethanol, dichloromethane, 1,2-
Dichloroethanes, chloroform, carbon tetrachloride, acetonitrile, oxolane, Isosorbide-5-Nitrae-dioxane, glycol dimethyl ether, or above solvent
The mixed solvent of composition；Reaction temperature is from 0 DEG C of any one steady state value, preferably room temperature to the reflux temperature of solvent.
The present invention also provides above-mentioned Fructus anacardii phenolic group cationic quaternary application in emulsion polymerization as emulsifying agent.?
When the compound of structural formula (i) carries out emulsion polymerization, monomer used is selected from acrylic compounds, methacrylic
One or more of compound, styrene compound；Initiator used is selected from sodium peroxydisulfate, potassium peroxydisulfate, persulfuric acid
One or more of ammonium, azodiisobutyronitrile.
Acrylic compounds of the present invention include sodium acrylate or acrylate, and the wherein ester of acrylate is first
Ester, ethyl ester, allyl ester, N-butyl or c1～c20The unitary alcohol ester of alkyl, binary alcohol esters or polyol ester；Described methacrylic acid
Class compound includes Sodium methacrylate. or methacrylate, and the wherein ester of methacrylate is methyl ester, ethyl ester, allyl ester
Or c1～c20The unitary alcohol ester of alkyl, binary alcohol esters or polyol ester；Described styrene compound includes styrene or replacement
The substituting group position of styrene, wherein substituted phenylethylene can be able to be unitary or polynary replacement, take in ortho position, para-position and meta
Can be c for base1～c18Alkyl, cycloalkyl, carboxyl or sulfonic group.
When the compound of structural formula (i) carries out emulsion polymerization, when monomer used contains allyl acrylate or methyl-prop
During olefin(e) acid allyl ester, gained homopolymer or copolymer and Fructus anacardii phenolic group cationic quaternary emulsifying agent, also can occur further
Photocuring reaction, obtains corresponding light-cured resin.
When the r in the compound of structural formula (i) is chlorine or bromine or iodine, the present invention also provides above-mentioned Fructus anacardii phenolic group cation
Type quaternary ammonium salt is simultaneously as emulsifying agent and application in emulsifier-free emulsion polymerization for atom transfer radical polymerization (atrp) initiator.
In carrying out emulsifier-free emulsion polymerization, other any emulsifying agents need not be added again.In emulsifier-free emulsion polymerization, monomer used is selected from third
One or more of alkene acid compounds, methacrylic compounds, styrene compound.
When carrying out emulsifier-free emulsion polymerization, part used is selected from nitrogenous or phosphorus-containing ligand；Wherein, containing n-donor ligand can be
But it is not limited to 2,2 '-bipyridine, n, n, n ', n '-tetramethylethylenediamine, five methyl diethylentriamine, three (2- dimethylaminos
Ethyl) amine, triethylenediamine (dabco), 1,8- diazabicylo 11 carbon -7- alkene (dbu), hexamethylenetetramine, n, n-
Dimethyl dodecylamine；Phosphorus-containing ligand can be but not limited to triphenylphosphine, three (4- aminomethyl phenyl) phosphine, three (4- methoxyl groups
Phenyl) phosphine；Used catalyst can be but not limited to cucl, cubr, cucl2、cubr2、cu(0)、fe(0)、fecl2、fecl3、
febr2、febr3.When catalyst is cucl2、cubr2、fecl3、febr3When, need in reaction to add reducing agent, reducing agent used
Ascorbic acid, sodium ascorbate, glucose, hydrazine hydrate, stannous octoate can be but not limited to.
When the present invention utilizes the compound of structural formula (i) to carry out emulsifier-free emulsion polymerization, the compound of structural formula (i) also can be joined
With radical polymerization, such that it is able to overcome, traditional small-molecular emulsifier is volatile, easy surface migration shortcoming.
When carrying out emulsifier-free emulsion polymerization using the compound of structural formula (i), the polymerization with structural formula (vii) can be obtained
Thing；And in this Living Radical Emulsion Polymerization reaction system, the unsaturated terminal chain of Cardanol is less or does not crosslink reaction,
And these unsaturated carbon carbon bond can carry out later photocuring or heat cure cross-linking reaction, thus can be applicable to photocureable coating or
In ink.
Wherein, the definition in m, x, t such as structural formula (i)；a1、a2、a3Each identical or different, independently selected from phenyl ,-
Coona or-coor1, described-coor1Ester can be the alkyl such as methyl, ethyl replace ester or the c having cycloalkyl substituted1~
c18Alkyl monocarbon alcohol ester, binary alcohol esters and polyol ester；e1、e2、e3Each identical or different, independently selected from methyl or hydrogen；
R=0～1000, u=0～1000, v=0～1000, y=0～1000, but r, u, y can not be zero simultaneously.
When the present invention utilizes the compound of structural formula (i) to carry out emulsifier-free emulsion polymerization, the compound of structural formula (i): monomer:
Catalyst: the mol ratio of part is=1:(1～1000): (0.1～10): (0.2～20)；It is preferably the chemical combination of structural formula (i)
Thing: monomer: catalyst: part=1:(5～500): (0.5～5): (0.5～10), polymer can be adjusted by changing proportioning
Molecular size range, molecular structure composition.The temperature of Raolical polymerizable of the present invention is 0～100 DEG C, suitable in order to reach
Response speed and save energy, reaction temperature be preferably 40 DEG C～70 DEG C.
The resin that the present invention is prepared by emulsifier-free emulsion polymerization when carrying out photocuring, used help light trigger can be but
It is not limited to michaelis ketone, triethylamine, tetramethylethylenediamine, diisopropyl ethyl amine, n, n- dimethyl dodecylamine, hexa-methylene
Tetramine, n, n- dimethylaniline, n, n- diethylaniline.
Fructus anacardii phenolic group cationic quaternary designed by the present invention, making full use of Cardanol, this is cheap renewable
On the basis of resource, can not only be used for atrp initiator, simultaneously after living polymerization gained linear polymer but also as photocuring
The prepolymer of resin.By adjusting Fructus anacardii phenolic group cationic quaternary and the ratio of monomer and the order of addition of monomer, can
Obtain the crosslinkable copolymer that molecular weight is controlled, molecular structure is controlled.The synthetic method of Fructus anacardii phenolic group cationic quaternary
Simply, easy and simple to handle, mild condition, prepared photocurable crosslinked polymer wide for suitable monomers scope when being polymerized,
Photocureable coating, the synthesis of ink, adhesive and other thermosetting resin have broad application prospects.
Specific embodiment
The present invention is expanded on further with reference to embodiment.It should be understood that these embodiments are merely to illustrate the present invention, and
It is not used in restriction the scope of the present invention.The experimental technique of the unreceipted actual conditions of the following example, generally according to normal condition, or
The condition that person provides according to manufacturer or advises.Unless otherwise indicated outer, all specialties used herein and scientific terminology with
Same meaning familiar to those skilled in the art.In addition any method similar or impartial to this method and material all can be used for
In the inventive method.
Embodiment 1
1) preparation of 4- brombutyl Fructus anacardii 2, 2-Oxydiphenol (iva)
By Isosorbide-5-Nitrae-dibromobutane (2.70g, 12.5mmol), sodium bicarbonate (8.4g, 100mmol) and oxolane (5ml)
Add in reaction bulb, then Cardanol (1.21g, 4mmol) is slowly added drop-wise in reactant mixture.After adding material, in room temperature
Under carry out etherification reaction, react 24h.Add 100ml water in system, point liquid, organic be added to anhydrous sodium sulfate drying, finally steam
Dry solvent obtains yellow oil.After crude product purified by silica gel column purification (eluant: ether/dichloromethane=1/1, volume ratio), obtain
Sterling (1.25g, 71%).
The sterling of gained is passed through 1h nmr and 13c nmr characterize, be 4- brombutyl Fructus anacardii 2, 2-Oxydiphenol, 1h nmr and 13c
The data of nmr is as follows.
1h nmr(400mhz,cdcl3):δ7.24-7.15(m,1h),6.83-6.71(m,3h),5.89-5.82(m,
0.3h), 5.49-5.34 (m, 3h), 5.12-5.00 (m, 0.6h), 4.02 (t, 2h, j=6.0hz), 3.54-3.44 (m, 5h),
2.88-2.81(m,2h),2.63(m,2h),2.16-2.00(m,8h),1.99-1.92(2h),1.66-1.57(m,2h),
1.43-1.26(m,12h),0.97-0.89(2h)；
13c nmr(100mhz,cdcl3):δ158.8,144.6,136.8,130.4,129.9,129.8,129.3,
129.1,127.6,126.8,120.9,114.7,111.3,66.6,36.0,33.6,32.6,31.4,31.0,29.8,29.6,
29.5,29.4,29.3,28.0,27.2,25.6,22.7,14.2.
2) preparation 4- (dimethylamino) normal-butyl Fructus anacardii 2, 2-Oxydiphenol (va)
Will be according to step 1) in 4- brombutyl Fructus anacardii 2, 2-Oxydiphenol (4.35g, 10mmol) that obtains be dissolved in oxolane
(100ml), it is then respectively adding natrium carbonicum calcinatum (5.0g), phase transfer catalyst tetrabutyl ammonium bromide (0.2g).Slowly drip again
Plus dimethylamine agueous solution 20ml, drip off rear room temperature reaction 5 hours, then flow back 2 hours.After the completion of reaction, boil off solvent, residue
Extracted three times with ethyl acetate, merge organic faciess, wash with water respectively, saturated common salt is washed, anhydrous sodium sulfate drying.Finally boil off
Solvent obtains final product product (3.23g, 81%).
The product of gained is passed through 1h nmr and 13c nmr characterize, be 4- (dimethylamino) normal-butyl Fructus anacardii 2, 2-Oxydiphenol, 1h
The data of nmr and 13c nmr is as follows.
1h nmr(400mhz,cdcl3):δ7.21-7.13(m,1h),6.77-6.70(m,3h),5.87-5.76(m,
0.29h), 5.46-5.27 (m, 2.74h), 5.07-4.96 (m, 0.62h), 3.96 (t, 2h, j=6.4hz), 2.86-2.73 (m,
1.58h), 2.56 (t, 2h, j=7.8hz), 2.33 (t, 2h, j=7.4hz), 2.23 (s, 6h), 2.08-1.94 (m, 3h),
1.81-1.72(m,2h),1.69-1.56(m,4h),1.39-1.21(m,12h),1.91-1.82(m,2h).
3) synthesize Gemini surface active agent 4,4 '-two [n, n- dimethyl-n- (4- Fructus anacardii phenolic group butyl) bromination ammonium first
Base] benzophenone (ia)
Under argon protection, sequentially add according to step 2 in reaction bulb) 4- (dimethylamino) the normal-butyl waist that obtains
Fruit 2, 2-Oxydiphenol (8.0g, 20mmol), 4,4 '-dibromo methyl benzophenone (3.68g, 10mmol), absolute ether 20ml.Reactant liquor returns
Stream 24 hours.Boil off ether and obtain crude product, then dissolved with methanol, add petroleum ether and stirring 5 hours, filter, obtain product
(9.22g, yield 79%).
By the Characterization of The Products of gained, it is 4,4 '-two [n, n- dimethyl-n- (4- Fructus anacardii phenolic group butyl) ammonium bromide ylmethyls]
Benzophenone, data is as follows:
M.p.84～86 DEG C
1h nmr(cdcl3): δ 7.86-7.83 (m, 4h), 7.75-7.73 (m, 8h), 7.62-7.56 (m, 2h), 7.49-
7.26(m,4h),7.13-7.08(m,2h),6.76-6.59(m,6h),6.84-6.72(m,0.65h),5.34-5.28(m,
5.55h), 5.22 (s, 4h), 5.04-4.91 (m, 1.5h), 3.98 (t, 4h, j=5.6hz), 3.69 (t, 4h, j=8.4hz),
3.37 (s, 12h), 2.82-2.71 (m, 4h), 2.50 (t, 6h, j=7.8hz), 2.11-1.93 (m, 10h), 4.91-4.83 (m,
5h),1.59-1.46(m,6h),1.39-1.21(m,31h),0.91-0.78(m,20h).
Embodiment 2
Synthetic surfactant 4- [n, n- dimethyl-n- (4- Fructus anacardii phenolic group butyl) ammonium methyl] -4 '-(bromomethyl) two
Benzophenone (ib)
The present embodiment prepares Fructus anacardii phenolic group cationic quaternary, step 1 according to the step of embodiment 1) and step 2) phase
Same, be in step 3 with the difference of embodiment 1) in:
Under nitrogen protection, sequentially add according to step 2 in reaction bulb) 4- (dimethylamino) the normal-butyl Fructus anacardii that obtains
2, 2-Oxydiphenol (4.0g, 10mmol), 4,4 '-dibromo methyl benzophenone (3.68g, 10mmol), dehydrated alcohol 20ml.Reactant liquor flows back
24 hours.Boil off ethanol and obtain crude product, add petroleum ether and stirring 5 hours, filter, obtain product (5.53g, yield 72%).
By the Characterization of The Products of gained, it is 4- [n, n- dimethyl-n- (4- Fructus anacardii phenolic group butyl) ammonium methyl] -4 '-(bromine first
Base) benzophenone, data is as follows.
M.p.43～45 DEG C
1h nmr(cdcl3): δ 7.89 (d, 4h, j=7.2hz), 7.60 (d, 4h, j=7.6hz), 7.08 (t, 1h, j=
8.4hz),6.70-6.61(m,3h),5.78-5.71(m,0.23h),5.37-5.22(m,2.9h),5.00-4.90(m,
0.49h),3.95(s,2h),3.73(s,2h),3.28(s,6h),2.78-2.69(m,2h),2.56-2.44(m,2h),2.11-
1.93(m,6h),1.88-1.80(m,2h),1.34-1.17(m,12h),0.88-0.79(m,2.18h).
Embodiment 3
Synthesis Gemini surface active agent 1,4- bis- [n, n- dimethyl-n- (4- Fructus anacardii phenolic group butyl) ammonium chloride ylmethyl] benzene
(ic)
The present embodiment prepares Fructus anacardii phenolic group cationic quaternary, step 1 according to the step of embodiment 1) and step 2) phase
Same, be in step 3 with the difference of embodiment 1) in:
Under nitrogen protection, sequentially add according to step 2 in reaction bulb) 4- (dimethylamino) the normal-butyl Fructus anacardii that obtains
2, 2-Oxydiphenol (8.0g, 20mmol), 4,4 '-two (chloromethyl) benzene (1.75g, 10mmol), anhydrous tetrahydro furan 30ml.Reactant liquor room temperature
Stirring 48 hours.Boil off thf and obtain crude product, then dissolved with ethanol, add acetonitrile and stir 8 hours, filter, obtain product
(9.14g, yield 86%).
By the Characterization of The Products of gained, it is Isosorbide-5-Nitrae-two [n, n- dimethyl-n- (4- Fructus anacardii phenolic group butyl) ammonium chloride ylmethyl]
Benzene, data is as follows:
M.p.53～54 DEG C
1h nmr(cdcl3):δ7.78(s,4h),7.21-7.13(m,2h),6.79-6.67(m,6h),5.87-5.76(m,
0.75h),5.48-5.29(m,10.4h),5.08-4.97(m,1.57h),4.05(s,4h),3.71-3.62(m,4h),3.27
(s,12h),2.86-2.75(m,4h),2.58-2.51(m,4h),2.13-1.96(m,14h),1.68-1.53(m,13h),
1.39-1.21(m,24h),0.92-0.85(m,3.85h).
Embodiment 4
Synthesis Gemini surface active agent 1,6- bis- [n, n- dimethyl-n- (4- Fructus anacardii phenolic group butyl) bromination ammonium] hexane
(id)
The present embodiment prepares Fructus anacardii phenolic group cationic quaternary, step 1 according to the step of embodiment 1) and step 2) phase
Same, be in step 3 with the difference of embodiment 1) in:
Under nitrogen protection, sequentially add according to step 2 in reaction bulb) 4- (dimethylamino) the normal-butyl Fructus anacardii that obtains
2, 2-Oxydiphenol (8.0g, 20mmol), 1,6- dibromo-hexane (2.44g, 10mmol), dimethoxy-ethane 30ml.Reactant liquor is at 50 DEG C
Stirring 12 hours.Boil off dme and obtain crude product, then dissolved with isopropanol, add hexamethylene and stir 6 hours, filter, produced
Thing (8.14g, yield 76%).
By the Characterization of The Products of gained, it is 1,6- bis- [n, n- dimethyl-n- (4- Fructus anacardii phenolic group butyl) bromination ammonium] hexane,
Data is as follows:
M.p.39～41 DEG C
1h nmr(cdcl3):δ7.23-7.17(m,2h),6.83-6.78(m,2h),6.75-6.569(m,4h),5.87-
5.83(m,0.81h),5.49-5.31(m,9.11h),5.10-4.98(m,1.65h),4.08-4.02(m,4h),3.81-3.73
(m,4h),3.69-3.62(m,4h),3.40(s,12h),2.88-2.78(m,4h),2.63-2.54(m,4h),2.11-1.82
(m,13h),1.67-1.58(m,8h),1.41-1.26(m,26h),0.93-0.87(m,4.2h).
Embodiment 5
Synthesis Gemini surface active agent 1,4- bis- [n, n- dimethyl-n- (4- Fructus anacardii phenolic group butyl) iodate ammonium] butane
(ie)
The present embodiment prepares Fructus anacardii phenolic group cationic quaternary, step 1 according to the step of embodiment 1) and step 2) phase
Same, be in step 3 with the difference of embodiment 1) in:
Under nitrogen protection, sequentially add according to step 2 in reaction bulb) 4- (dimethylamino) the normal-butyl Fructus anacardii that obtains
2, 2-Oxydiphenol (10.0g, 25mmol), Isosorbide-5-Nitrae-two iodobutane (3.10g, 10mmol), Isosorbide-5-Nitrae-dioxane 30ml.Reactant liquor is at 50 DEG C
Stirring 12 hours.Boil off Isosorbide-5-Nitrae-dioxane and obtain crude product, then dissolved with the tert-butyl alcohol, add pentane and stir 6 hours, mistake
Filter, obtains product (8.26g, yield 83%).
By the Characterization of The Products of gained, it is Isosorbide-5-Nitrae-two [n, n- dimethyl-n- (4- Fructus anacardii phenolic group butyl) iodate ammonium] butane,
Data is as follows:
1h nmr(cdcl3):δ7.27-7.19(m,2h),6.87-6.73(m,6h),5.91-5.82(m,0.90h),
5.51-5.36(m,8.03h),5.14-5.00(m,1.91h),4.11-4.05(m,4h),3.86-3.79(m,4h),3.73-
3.68(m,4h),3.46(s,12h),2.88-2.81(m,4h),2.66-2.58(m,4h),2.12-1.91(m,13h),1.74-
1.60(m,7h),1.45-1.28(m,24h),0.98-0.89(m,4.45h).
Application Example 1
4,4 '-two [n, n- dimethyl-n- (4- Fructus anacardii phenolic group butyl) ammonium methyl] hexichol first using embodiment 1 preparation
Ketone (ia) carries out the emulsion copolymerization of butyl acrylate (ba) and allyl methacrylate as emulsifying agent
Under nitrogen protection, reaction bulb sequentially adds butyl acrylate (1.92g, 15mmol), methacrylic acid allyl
Ester (1.89g, 15mmol), 4,4 '-two [n, n- dimethyl-n- (4- Fructus anacardii phenolic group butyl) ammonium methyl] benzophenone (ia)
(0.1g), potassium peroxydisulfate (0.39g, 1.71mmol) and deionized water (20ml).Mixed liquor is first in room temperature and high-speed stirred condition
Lower pre-emulsification 30min, is then heated to 70 DEG C in a water bath and keeps constant temperature.After 5h, stopped reaction, add first after emulsion cooling
Alcohol carries out precipitation process.
Gel permeation chromatography (gpc) measures molecular weight mn,gpc=4380；Molecular weight distribution pdi=2.28.
Application Example 2
Emulsion using Application Example 1 preparation carries out uv solidification
Reactive diluent ethylene glycol diacrylate will be added in emulsion according to the method preparation of Application Example 1
0.212g, help light trigger n, n- dimethyl dodecylamine 0.2g, after stirring, uniformly paving on a glass, after then drying
Obtain polymeric film 3.22g.This polymeric film is carried out irradiation under the uv light of 365nm, after 30min, determines sample with fingers-touch method
Reach tack, stopped illumination, obtain the light-cured resin of allyl methacrylate and butyl acrylate copolymer.
Application Example 3
Carry out the emulsifier-free emulsion polymerization of methyl methacrylate (mma) using the 2-in-1 forming surfactants of embodiment (ib)
Under nitrogen protection, reaction bulb sequentially adds methyl methacrylate (3.0g, 30mmol), 4- [n, n- diformazan
Base-n- (4- Fructus anacardii phenolic group butyl) ammonium methyl] -4 '-(bromomethyl) benzophenone (ib) (2.06g, 3mmol), cubr2
(0.223g, 1mmol), 2,2 '-bipyridine (0.31g, 2mmol) and deionized water (20ml).Mixed liquor is first in room temperature and height
Pre-emulsification 30min under fast stirring condition, is subsequently adding sodium ascorbate (0.5g), reactant liquor is heated in oil bath 70 DEG C simultaneously
Keep constant temperature.After 4h, stopped reaction, add methanol to carry out precipitation process after emulsion cooling.
Theoretical molecular mn,th=1580；Gel permeation chromatography (gpc) measures molecular weight mn,gpc=1920；Molecular weight distribution
Pdi=1.19.
Application Example 4
Emulsion using Application Example 3 preparation carries out uv solidification
Reactive diluent 3- tri- (acryloxy) propane will be added in emulsion according to the method preparation of Application Example 3
After 0.352g, stirring, uniformly paving on a glass, obtains polymeric film 2.92g after then drying.By this polymeric film in 365nm
Uv light under carry out irradiation, after 20min, determine that sample has reached tack with fingers-touch method, stop illumination, obtain Cardanol ylmethyl
The light-cured resin of acrylic acid methyl ester..
Claims (10)
1. a kind of Fructus anacardii phenolic group cationic quaternary is it is characterised in that structural formula such as following formula (i):
Wherein, r be chlorine, bromine, iodine,One of；T is c2～c10Alkyl, o-, m-, to dimethylene benzene,
One of 4,4 '-dimethylene benzophenone；M=2～10；N=0～6；X=chlorine, bromine or iodine.
2. the preparation method of Fructus anacardii phenolic group cationic quaternary according to claim 1 is it is characterised in that methods described
Comprise the steps:
1) dihalide of structural formula (ii) and Cardanol (iii) are carried out etherification reaction under alkali and solvent condition, tied
The compound of structure formula (iv)；
2) compound of structural formula (iv) is reacted with dimethylamine, obtain the compound of structural formula (v)；
3) compound of the compound of structural formula (v) and structural formula (vi) is reacted, obtain the product of structural formula (i)；
Reaction scheme is as follows:
Wherein, r be chlorine, bromine, iodine,One of；T is c2～c10Alkyl, o-, m-, to dimethylene benzene,
One of 4,4 '-dimethylene benzophenone；M=2～10；N=0～6；X=chlorine, bromine or iodine.
3. Fructus anacardii phenolic group cationic quaternary according to claim 2 preparation method it is characterised in that: step 1)
In, dihalide used is selected from 1,2- dichloroethanes, glycol dibromide, 1,3- dichloropropane, 1,3- dibromopropane, 1,3- bis-
Iodopropane, 1,4- dibromobutane, pentamethylene bromide, 1,5- bis- iodopentane, 1,6- dibromo-hexane or 1,10- dibromo-decane；Institute
It is selected from sodium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, triethylamine, diisopropyl ethyl with alkali
Amine, pyridine, n, n- dimethyl dodecylamine, tetramethylethylenediamine or n, n- dimethylethanolamine；Solvent for use be selected from acetone,
Dichloromethane, 1,2- dichloroethanes, chloroform, carbon tetrachloride, acetonitrile, oxolane, 1,4- dioxane, benzene, toluene or diformazan
Benzene；Reaction temperature is room temperature.
4. Fructus anacardii phenolic group cationic quaternary according to claim 2 preparation method it is characterised in that: step 2)
In, dimethylamine used by reaction can be aqueous solution can also be its hydrochlorate, hydrobromate or hydriodate；Add during reaction simultaneously
Enter other alkali, other alkali used is selected from sodium carbonate, potassium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide or potassium phosphate；Reaction institute
With solvent selected from acetone, dichloromethane, 1,2- dichloroethanes, chloroform, carbon tetrachloride, acetonitrile, oxolane, 1,4- dioxy six
Ring or be above solvent composition mixed solvent；Reaction temperature is room temperature.
5. Fructus anacardii phenolic group cationic quaternary according to claim 2 preparation method it is characterised in that: step 3)
In, reaction solvent for use be selected from acetone, ether, ethanol, dichloromethane, 1,2- dichloroethanes, chloroform, carbon tetrachloride, acetonitrile, four
Hydrogen furan, Isosorbide-5-Nitrae-dioxane, glycol dimethyl ether, or the mixed solvent of above solvent composition；Reaction temperature is room temperature.
6. Fructus anacardii phenolic group cationic quaternary application in emulsion polymerization as emulsifying agent according to claim 1,
It is characterized in that: when the compound of structural formula (i) carries out emulsion polymerization, monomer used be selected from acrylic compounds,
One or more of methacrylic compounds, styrene compound；Initiator used is selected from sodium peroxydisulfate, mistake
One or more of potassium sulfate, Ammonium persulfate., azodiisobutyronitrile.
7. Fructus anacardii phenolic group cationic quaternary application in emulsion polymerization as emulsifying agent according to claim 6,
It is characterized in that: described acrylic compounds include sodium acrylate or acrylate, and the wherein ester of acrylate is methyl ester, second
Ester, allyl ester, N-butyl or c1～c20The unitary alcohol ester of alkyl, binary alcohol esters or polyol ester；Described methacrylic
Compound includes Sodium methacrylate. or methacrylate, and the wherein ester of methacrylate is methyl ester, ethyl ester, allyl ester or c1
～c20The unitary alcohol ester of alkyl, binary alcohol esters or polyol ester；Described styrene compound includes styrene or substituted benzene second
The substituting group position of alkene, wherein substituted phenylethylene can be able to be unitary or polynary replacement in ortho position, para-position and meta, substituent group
Can be c1～c18Alkyl, cycloalkyl, carboxyl or sulfonic group.
8. Fructus anacardii phenolic group cationic quaternary according to claim 1 is as emulsifying agent and atom transfer radical polymerization
Initiator in the application in emulsifier-free emulsion polymerization it is characterised in that: when the r in the compound of structural formula (i) be chlorine or bromine or iodine
When, the compound of structural formula (i) is simultaneously as emulsifying agent and atom transfer radical polymerization initiator in emulsifier-free emulsion polymerization
Application.
9. Fructus anacardii phenolic group cationic quaternary according to claim 8 is as emulsifying agent and atom transfer radical polymerization
Application in emulsifier-free emulsion polymerization for the initiator it is characterised in that: carry out emulsifier-free emulsion polymerization in the compound of structural formula (i)
When, part used is selected from nitrogenous or phosphorus-containing ligand；Wherein, containing n-donor ligand is selected from 2,2 '-bipyridine, n, n, n ', n '-tetramethyl
Base ethylenediamine, five methyl diethylentriamine, three (2- dimethylaminoethyl) amine, triethylenediamine (dabco), 1,8- phenodiazine
Miscellaneous bicyclo- 11 carbon -7- alkene (dbu), hexamethylenetetramine, n, n- dimethyl dodecylamine；Phosphorus-containing ligand is selected from triphenyl
Phosphine, three (4- aminomethyl phenyl) phosphine, three (4- methoxyphenyl) phosphine；Used catalyst is selected from cucl, cubr, cucl2、cubr2、cu
(0)、fe(0)、fecl2、fecl3、febr2、febr3.
10. Fructus anacardii phenolic group cationic quaternary according to claim 9 gathers as emulsifying agent and atom transferred free radical
Close application in emulsifier-free emulsion polymerization for the initiator it is characterised in that: when catalyst is cucl2、cubr2、fecl3、febr3When,
Need in reaction to add reducing agent, reducing agent used is selected from ascorbic acid, sodium ascorbate, glucose, hydrazine hydrate, octanoic acid Asia
Stannum.
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| CN107321263B (en) * | 2017-07-31 | 2021-11-12 | 上海邦高化学有限公司 | Cardanol cationic surfactant and preparation method and application thereof |
| CN107694358A (en) * | 2017-09-22 | 2018-02-16 | 同济大学 | A kind of preparation method of the anti-bacterial and anti-fouling dyeing polymer seperation film based on surface grafting |
| CN108658846B (en) * | 2018-06-12 | 2021-03-26 | 上海邦高化学有限公司 | Quaternary ammonium salt containing cardanol group and application thereof |
| CN110590581A (en) * | 2019-09-06 | 2019-12-20 | 天津理工大学 | Cardanol-based aqueous phase dispersing auxiliary agent for improving carbon nano tube aqueous phase sterilizing capability and synthesis method thereof |
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